Sodium hydride → HCID 21997632, compound

HRID 1977105Notes

Reaction equation

HRID 1977105 reaction equation
[H-].[Na+].[NH2:3][C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[CH:6][C:5]=1[SH:14].I[CH2:16][C:17]#[N:18]>CN(C)C=O>[NH2:3][C:4]1[CH:9]=[C:8]([C:10]([F:11])([F:12])[F:13])[CH:7]=[CH:6][C:5]=1[S:14][CH2:16][C:17]#[N:18]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 69356IodoacetonitrileHCID 880422-Amino-4-(trifluoromethyl)benzenethiol

Product 1

HCID 21997632HCID 21997632, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Sodium hydride (2.93 g, 60% dispersion in mineral oil) was added at 5-10° C. under nitrogen in small portions to a stirred and cooled solution of 2-amino-4-trifluoromethyl-benzenethiol (8.00 g) dissolved in dry dimethylformamide (125 ml). After stirring for 45 min iodoacetonitrile (2.65 ml) was added. Stirring was continued at ˜0° C. for 15 min and then at room temperature for 1 h. The mixture was concentrated in vacuo at 55° C. and the oily residue was extracted with petroleum ether (3×50 ml) in order to remove the mineral oil. The residue was partitioned between water (50 ml) and ethyl acetate (100 ml). The organic phase was washed with water (2×50 ml) and then with brine (30 ml), dried over sodium sulfate, filtered and concentrated in vacuo to give a yellow oil. The crude product was purified by flash chromatography on silica gel eluted with ethyl acetate-heptane 3:7 giving the title compound as a yellow oil. Yield 6.1 g (75%); 1H-NMR (DMSO-d6) δ (ppm): 7.54 (d, J=8.3 Hz, 1H), 7.09 (d, J=1.8 Hz, 1H), 6.86 (dd, 1H), 5.97 (br, 2H), 4.02 (s, 2H); 13C-NMR (DMSO-d6) δ (ppm): 150.0, 135.7, 130.8 (q, J=31 Hz), 124.2 (q, J=272 Hz), 117.7, 117.1, 112.1 (q, J=3.8 Hz), 110.6 (q, J=3.9 Hz), 18.1.

Workup

  1. additionwas added
  2. stirringStirring
  3. waitat room temperature for 1 h
  4. concentrationThe mixture was concentrated in vacuo at 55° C.
  5. extractionthe oily residue was extracted with petroleum ether (3×50 ml) in order
  6. customto remove the mineral oil
  7. customThe residue was partitioned between water (50 ml) and ethyl acetate (100 ml)
  8. washThe organic phase was washed with water (2×50 ml)
  9. dry with materialwith brine (30 ml), dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customto give a yellow oil
  13. customThe crude product was purified by flash chromatography on silica gel
  14. washeluted with ethyl acetate-heptane 3:7 giving the title compound as a yellow oil

Sources & evidence

ORD record
ord-d3bc7481edf7461bb4b45c8a4c08b313
Source dataset
uspto-grants-2001_05
Patent number
US06232310B1

Reaction notes

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